Method of treating liquid partial-oxidation products



Patented Apr. 8, 1930 UNITED STATES PATENT OFFICE JOSEPH EIIDY TAKES, OF PITTSBURGH, PENNSYLVANIA, ASSIGHOB TO P.

BYBNES, TRUSTEE, OI SEWICKLEY, PENNSYLVANIA' HE'IEOI) OI EBEATI'N LIQUID PABTIALOXIDA'IIOH PRODUCTS Io Drawing. Original application filed larch 1, 1919, serial No. 281,195." Divided and um app1ieatioa med July a, 1983.

This application forms a division of my copending application Serial No. 281,197, filed March 7, 1919, for Method of treating aldehyde fatty acid mixturesand products 5 thereof.

In that and earlier appli ations, such as Serial No. 272,567, Ihave described partial i "combustion or oxidation methods for producing aldehyde fatty acids from ordinary liquid hydrocarbons occurring in petroleum, shale oil, or oils'produced by the low temperature distillation of bituminous or cannel coals.

In such methods the liquid hydrocarbon is:

vaporized, mixed with air or an oxygen-containing gas in regulated proportions, near the theoretical combining proportion or preferably in excess thereof; and the hot mixture is passed, with-or without the addition ofa diluting-gas such as steam, through a rela-.

3. tively thin layer or through successive relatively thin layers of catalytic material under a regulated temperature, preferably below 7 500 C. The catalysts employed are preferably complex oxides or compounds of metals having a varying valence, such, for ex;

ample, as the blue oxidesof molybdenum.

i The products of this partial combustion or partial oxidation process are then condensed,

giving a mixture of .partial oxidation products, ranging from alcohols, through-aldehydes or aldehyde fatty acids. The process may be varied to roduoe more or less of the v Per cent Aldehyde fatty acids Aldehydes V ,25 Hydrocarbons and undeterm1ned; 5

These substances are soluble in each other througha wide range of proportions. i The object of the presentinvention is to separate the aldehyde fatty acids from the mixture and form industrial or commercial "products from the acids and other consti'-- tuents. In thepreferred-form of my method will a longer time. the production of compounds of the acids Serial No. 41,285.

and their separation from the rest of the mixture, are carried out in thesame steps, though they may be carried out separately aslater set forth.

In the I referred form, metallic salts (either solu 1e or insoluble) of the aldehyde fatty acids are formed; and the residual aldehydes and hydrocarbons are preferably returned for conversion into aldeh de fatty acids by the process of the ap ications a ove referred to. For exam le,i insoluble or slightly soluble soa s are esire'd, the solution or mixture of al ehyde fatty acids, a1- dehydes and hydrocarbons is agitated (preferably hot) withthe hydroxide of the metal (such as, lead or aluminum) until the aldehyde fatty acids have combined to form an insoluble or slightly soluble metallic soap.

If a soluble salt of the metal is used, the reaction will be more rapid at first, but onaccount of the liberation of free mineral acid, metallic hydroxide should be added from time to time for its neutralization. The soap is then removed, as, for example, by filterin and'the residual solution or mixture .o aldehydes, hydrocarbons, etc.,' is recovered.

A' more rapid form of the above method is obtained b adding a suflicient quantity of a a solvent, suc as alcohol, to'di 'ssolve both the mixture and the metallicsalt added. This solvent should be added before the metallic hydroxide (or metallic salt andmetallic hydroxide) is added as above. When the reaction is completed (which may be hastened by warming), the alcohol is easily. distilled off and the soaps removed by filtration or decantation; v

When solublealkali metal soaps of the aldehyde fatty .acids are desired, such as sodium soapzor potassium soa the original mixture, containing series 0 aldehyde fatty acids, aldehydes and hydrocarbons, is agitated with a water solution of the hydroxide, carbonate, or bicarbonate of the alkali metal. Heating obtained in the soap by carrying out the reactions at 'ordinarwyhtemperatures, this taking en the reaction of neutralization has proceeded sufiiciently near to as'ten the reaction, but a better color is completion, the agitation is stopped and the two liquids separate into layers.

The water solution-of the aldehyde fatty acid soap comprising the lower layer can be drawn off, leaving the solution mixture of aldehydes, hydrocarbons, etc.

I may cause a more rapid saponification by first dissolving the original mixture of alde- I hyde fatty acids, aldehydes and hydrocarbons in alcohol and adding, either in the solid form or in a water solution or alcoholic solution, the carbonate, hydroxide, or bicarbonate of the desired alkali metal to be used.

\ economic procedure for separating the aldehyde fatt acids in the form of their alkaline meta salts (soa -In this process, the

. reaction mixture (al ehyde fatty acids, aldehydes, hydrocarbons, etc.) is heated to a suitable temperature, say above 100 C., with the addition of dry solid hydroxide, carbonate or bicarbonate of the particular metal, the salt of which is desired. The mixture is preferably agitated during this step, either by mechanical or convection current devices.

The soap' formed in this reaction will largely separate from the mixture on cooling, and can be removed mechanically, fresh mixture being added and the treatment continued as lon as possible. The non-saponifiable matter is preferably taken back to the oxidation process for re-t-reatment into aldehyde fatty acids.

In the same manner (dry additions with beating), I can prepare insoluble metallic soa the addition in this case being prefera ly that of ap roximately equimolecular pro ortions of t e chloride or other salt of t 1e metal and the hydroxide. The metallic soap separating on cooling canbe easily removed mechanically and the treatment continued with fresh additions of the mixture as long as practicable.

The calcium soap produced from aldehyde fatty acids which are soluble in water are especially valuable, having, approximately the same solubility as the sodium soaps of higher fatty acids.

In the above examples, the acid compounds are formed before or during separation from the aldehydes, hydrocarbons, etc. I may, however, within my broader claims, separate the aldehyde fatty acids from the remainder of the ori inal mixture before forming their compoun s. Thus, I may distill off the aldehydes and hydrocarbons, which are more volatile than the aldehyde fatty acids, and then treat the separate acids to form their compounds. The distillation may be carried out with or without the aid of steam or other diluent. V

In this divisional case I intend to cover the steps of removing at least a part of the acids from the original condensed liquid product mixture and then returning at least a part of thewemaining liquid for further partial oxidation treatment substantially the same as that originally used on the li uid hydrocarbons. Here again a portion 0 the product is vaporized, mixed withoxygen and assed through a conversion. zone, {prefera ly in the presence of catalysts such as those named, at a temperature below a red heat, thus giving a further conversion of the already partly oxidized material. I also intend to cover removing some of the constituents .of the partialoxidation product mixture and further oxidizing part of the separated constituents,

whether in the vapor phase as above described or in other ways.

Many variations may be made in carrying out theprocess without departing from my invention, as defined in the claims. 4

I claim:

1. The method of treating a partial oxidation product of mineraloil'containing -alde-' hyde fatty acids, consisting in separating atleast a material portion of the acids from the other constituents of the partial oxidation product, and subjecting atleast a material portion of the other constituents to partial oxidation with oxygen while in the vapor ase.

p 2. The method of treating a partial oxida tion product of mineral oil containin aldehyde fatty acids, consisting in separating the free acids from the other constituents, and

jss

subjecting ,other constituents to partial'oxidation with oxygen while in the vapor phase. 3. The method of treating a partial. oxidation product of mineral oil containing aldehyde fatty acids, consisting in forming metallic soaps of the acids, separating these soaps, and subjecting other constituents to partial oxidation with oxygen while in the vapor phase. a

4. In the treatment of a mixture of hydrocarbons including aliphatic hydrocarbons which already contain artificially-introduced chemically-combined oxygen to different de-' grees of oxidation, the steps consisting of separating more highly oxidized bodies from less highly oxidized bodies, and then further partially oxidizing some of the separated less highly oxidized bodies.

5. The meth d of treating a partial oxidation product of mineral oil containing aldehyde fatty acids, consisting in separating part of the constituents from the other constituents of the partial oxidation product, and

further oxidizing some of the separated constituents.

6. The method of treating a partial oxidation product of mineral oil, containing aldehyde fatty acids, consisting in separating at least a material portion of the acids from the other constituents of the partial oxidation product, and subjecting at least a material portion of the other constituents to partial oxidation. I

7. In the treatment of a partial oxidation product containing alcohols, aldehyde-like bodies, and acids, the steps consisting of separating more highly oxidized bodies from less highly oxidized bodies, and further partially oxidizing some of the separated less highly oxidized bodies 8. In the treatment of a mixture of hydrocarbons including aliphatic hydrocarbons which already contain artificially-nitroduced chemically-combined oxygen to difierent degrees of oxidation, the steps consisting of separating more highly oxidized bodies from less highly oxidized bodies, chemically treating some of the more highly oxidized bodies, and further partially oxidizing some of the separated less highly oxidized bodies.

In testimony whereof I have hereunto set m hand.

JOSEPH HIDY JAMES. 

